Photolysis Reactions Research Articles

Expanding the Color Range of Photoresponsive Multicolor Luminescent System Through Host-Guest Interaction.

Photoresponsive multicolor luminescent systems offer interesting functions, which have led to applications in anticounterfeiting and biological imaging. However, expanding the color range of these materials remains a challenging task. Herein, a carbazole-modified dithienylethene derivative (DTE-CZ) that exhibits modulated fluorescence color changes through the photocyclization reaction and photolysis reaction is synthesized. DTE-CZ emits orange fluorescence, and it can release a fluorophore which emits blue fluorescence by the photolysis reaction, resulting in the color change. Upon complexation of DTE-CZ with cucurbit[10]uril (CB[10]), the fluorescence wavelength will have a blue shift and the photolysis reaction will be inhibited. Benefiting from the influence of CB[10] and the photolysis reaction of free guests, the color range of the photoresponsive system which is composed of free guests and host-guest complexes is further extended. White light emission along with a color shift from yellow-green to blue was achieved by adjusting the ratio of free guests to host-guest complexes. Finally, the photoresponsive multicolor systems are utilized to construct a photostimulated PVA film and an information encryption system. This work provides an alternative strategy for the preparing of photoresponsive multicolor luminescent system and modulation of its color range.

Coumarin-Derived Caging Groups in the Spotlight: Tailoring Physiochemical and Photophysical Properties.

The development of light-responsive molecular tools enables spatiotemporal control of biochemical processes with superior precision. Amongst these molecular tools, photolabile caging groups are employed to prevent critical binding interactions between a bioactive molecule and its corresponding target. Only upon irradiation with light, the bioactive is released in its 'active' form and is now readily available to bind to its target. Coumarin-derived caging groups constitute one of the most popular classes of photolabile protecting groups, due to their facile synthetic accessibility, ease of tuning photophysical properties via structural modification and rapid photolysis reactions. Herein, we highlight the recent progress made on the development of coumarin-derived caging groups, in which the red-shifting of absorption spectra, improving aqueous solubility and tailoring sub-cellular localisation has been of particular interest.

Reactivity of [(Cp*CoPh)(Cp*Co)(μ-TePh)(μ-k2-Te,H-TeBH3)] Toward [M(CO)5·THF] (M = Mo and W), CS2, and [Fe2(CO)9

Syntheses and structural elucidation of homo- and heterochalcogen-bridged complexes of cobalt are described. The photolytic reaction of bimetallic hydridoborate species [(Cp*CoPh)(Cp*Co)(μ-TePh)(μ-k2-Te,H-TeBH3)] (1) in the presence of [M(CO)5·THF] (M = Mo and W) afforded unprecedented tellurolate-bridged [(Cp*Co)2(μ-TePh)3]+[TePh{M(CO)5}2]- (M = Mo (2), W (3)) as ionic complexes with the release of BH3. Complex 2 has three bridged-TePh moieties between two Cp*Co fragments in the cation part, whereas the anionic part, [TePh{M(CO)5}2]-, shows a distorted trigonal pyramidal core. In order to synthesize mixed chalcogenate-bridged complexes having both S and Te, we carried out the photolytic reaction of 1 with CS2. Although the objective of generating mixed chalcogen-bridged complex [(Cp*Co)2(μ-TePh)2(μ-S)] was not achieved, the reaction yielded an unusual bimetallic thiotellurite complex [(Cp*Co)2(μ-S3TeS3-κ2S:κ2Te:κ2S')] (4). Complex 4 has two wings, each consisting of three sulfur atoms, that are connected to two Co-atoms and one Te-atom. Further, to synthesize the Fe analogue of 2 and 3, a similar reaction was carried out with [Fe2(CO)9]. However, the reaction led to the formation of the trimetallic complex [Cp*Co(CO)(μ3-Te)2{Fe2(CO)6}] (5). These complexes were characterized by employing different multinuclear NMR, IR spectroscopies, single-crystal X-ray diffraction analyses, and mass spectrometry. Additionally, computational analyses of these chalcogen-bridged neutral and ionic complexes were conducted to offer insight into their bonding.

Photolysis of dinotefuran and nitenpyram in water and ice phase: Influence mechanism of temperature over photolysis

Neonicotinoids are widely used pesticides around the world, but the photolysis of neonicotinoids in cold agricultural region are still in blank. This paper aimed to study the influence of cold temperature over photolysis of neonicotinoids. To this end, the photolysis rates and photoproducts of dinotefuran and nitenpyram in water, ice and freeze-thawing condition were determined. Coupled with quantum chemistry calculation, the influence mechanisms of temperature and medium were investigated. The results showed the photolysis rates of neonicotinoids in water condition slightly declined with the lowered temperature due to the photolysis reactions were endothermic reactions. However, the photolysis rates increased by 89.8 %, 59.2 %, 49.4 % and 9.5 % for dinotefuran and nitenpyram in ice and thawing condition, respectively. This phenomenon was posed by the concentration-enhancing effect and change of photo-chemical properties of neonicotinoids in ice condition, which included lowered bond cleavage energy, lowered first excited singlet state energy and expanded light absorption range. The photolysis pathways of the two neonicotinoids did not change in different medium, but the concentration of carboxyl products was relatively higher than that of water condition due to the more amounts of reactive oxygen species in ice medium, which might increase the secondary pollution risk after ice-off in spring due to the higher ecotoxicity to nontarget organism of these photoproducts. The influence of cold temperature and medium change should be considered for the environmental fate and risk assessment of neonicotinoids in cold agricultural region.

Catalytic and Selective Red Light-Triggered Photodegradation of a G-Quadruplex DNA by a Zinc (II) Phthalocyanine.

Water-soluble phthalocyanine (Pc) derivatives have been regarded as potential G-quadruplex (G4) nucleic acid-targeting ligands for anticancer therapy and have been extensively studied as effective photosensitizers for photodynamic therapy (PDT). Understanding how photosensitizers interact with nucleic acids and the subsequent photolytic reactions is essential for deciphering the initial steps of PDT, thereby aiding in the development of new photosensitizing agents. In this study, we found that red-light irradiation of a mixture of a Zn(II) Pc derivative and an all-parallel G4 DNA leads to catalytic and selective photodegradation of the DNA by reactive oxygen species (ROS) generated from the Zn(II) Pc derivative bound to DNA through a reaction mechanism similar to that of an enzyme reaction. This finding provides a novel insight into the molecular design of a photosensitizer to enhance its PDT efficacy.

A comprehensive study on three typical photoacid generators using photoelectron spectroscopy and abinitio calculations.

Conducting a comprehensive molecular-level evaluation of a photoacid generator (PAG) and its subsequent impact on lithography performance can facilitate the rational design of a promising 193nm photoresist tailored to specific requirements. In this study, we integrated spectroscopy and computational techniques to meticulously investigate the pivotal factors of three prototypical PAG anions, p-toluenesulfonate (pTS-), 2-(trifluoromethyl)benzene-1-sulfonate (TFMBS-), and triflate (TF-), in the lithography process. Our findings reveal a significant redshift in the absorption spectra caused by specific PAG anions, attributed to their involvement in electronic transition processes, thereby enhancing the transparency of the standard PAG cation, triphenylsulfonium (TPS+), particularly at ∼193nm. Furthermore, the electronic stability of PAG anions can be enhanced by solvent effects with varying degrees of strength. We observed the lowest vertical detachment energy of 6.6eV of pTS- in PGMEA solution based on the polarizable continuum model, which prevents anion loss at 193nm lithography. In addition, our findings indicate gas-phase proton affinity values of 316.4 kcal/mol for pTS-, 308.1 kcal/mol for TFMBS-, and 303.2 kcal/mol for TF-, which suggest the increasing acidity strength, yet even the weakest acid pTS- is still stronger than strong acid HBr. The photolysis of TPS+-based PAG, TPS+·pTS-, generated an excited state leading to homolysis bond cleavage with the lowest reaction energy of 83 kcal/mol. Overall, the PAG anion pTS- displayed moderate acidity, possessed the lowest photolysis reaction energy, and demonstrated an appropriate redshift. These properties collectively render it a promising candidate for an effective acid producer.

Preparation and Optical and Electrochemical Properties of Boron (III) Octafluorosubphthalocyanines with One Triselenole and One Diselenet Ring.

Unsymmetric boron (III) subphthalocyanines with a triselenole ring or a diselenete ring and eight fluoro groups were prepared by the reaction of 5,6-dicyano-4,7-diethylbenzo-[1,2,3]triselenole and tetrafluorophthalonitrile with trichloroborane in xylene. The reaction was accompanied by a contraction of the triselenole ring to the diselenete ring. The substrate, dicyanobenzo[1,2,3]triselenole, was prepared by a new procedure via a photolytic demethylenation reaction of 3,7-diethyl[1,3]diselenolophthalonitrile using a 10 W white LED light. While triselenolosubphthalocyanine was treated by triphenylphosphine to give the diselenete derivative, the reaction of diselenetosubphthalocyanine with Woolion's reagent produced the expanded triselenole ring. The diselenete derivative reacted with tetrakis(triphenylphosphine)platinum to yield the corresponding platinum complex with Se-Pt bonds. Q-band absorption for the products appeared at around λmax=590 nm in the UV-vis spectrum and weak emission was observed at about λe=620 nm. When diselenetosubphthalocyanine was treated with pentachloro antimonate in dichloromethane or sodium metal in hexane/tetrahydrofuran, the solution showed strong ESR signals. The structures of model compounds were optimized using the DFT method with the Gaussian 09 program at the B3LYP/6-31G (d, p) level.

Development of the adjoint of the unified tropospheric–stratospheric chemistry extension (UCX) in GEOS-Chem adjoint v36

Abstract. Atmospheric sensitivities (gradients), quantifying the atmospheric response to emissions or other perturbations, can provide meaningful insights on the underlying atmospheric chemistry or transport processes. Atmospheric adjoint modeling enables the calculation of receptor-oriented sensitivities of model outputs of interest to input parameters (e.g., emissions), overcoming the numerical cost of conventional (forward) modeling. The adjoint of the GEOS-Chem atmospheric chemistry-transport model is a widely used such model, but prior to v36 it lacked extensive stratospheric capabilities. Here, we present the development and evaluation of the discrete adjoint of the global chemistry-transport model (CTM) GEOS-Chem unified chemistry extension (UCX) for stratospheric applications, which extends the existing capabilities of the GEOS-Chem adjoint to enable the calculation of sensitivities that include stratospheric chemistry and interactions. This development adds 37 new tracers, 273 kinetic and photolysis reactions, an updated photolysis scheme, treatment of stratospheric aerosols, and all other features described in the original UCX paper. With this development the GEOS-Chem adjoint model is able to capture the spatial, temporal, and speciated variability in stratospheric ozone depletion processes, among other processes. We demonstrate its use by calculating 2-week sensitivities of stratospheric ozone to precursor species and show that the adjoint captures the Antarctic ozone depletion potential of active halogen species, including the chlorine activation and deactivation process. The spatial variations in the sensitivity of stratospheric ozone to NOx emissions are also described. This development expands the scope of research questions that can be addressed by allowing stratospheric interactions and feedbacks to be considered in the tropospheric sensitivity and inversion applications.

Products from Photolysis Reactions of Tetracycline Mediated by Clay and Humic Substance Induce Contrasting Expressions of Target Resistance Genes.

Phototransformation is a key process affecting the fate of many antibiotics in the environment, but little is known about whether their photoproducts exert selective pressure on bacteria by inducing antibiotic resistance genes (ARGs). Here, we examined the expression of tetracycline resistance gene tet(M) of a fluorescent Escherichia coli whole-cell bioreporter influenced by the phototransformation of tetracycline. The presence of suspended smectite clay (montmorillonite or hectorite, 1.75 g/L) or dissolved humic substance (Pahokee Peat humic acid or Pahokee peat fulvic acid, 10 mg C/L) in aqueous solutions markedly facilitated the transformation of tetracycline (initially at 400 μg/L) with half-life shortened by 1.4-2.6 times. Despite the similar phototransformation ratios (80-90%) of the total loaded tetracycline after 60 min irradiation, the decreased ratios of cell fluorescence intensity (which was proportional to the expression amount of ARG tet(M)) were much higher with the two clays (94 and 93%) than with the two humic substances (44 and 69%) when compared to the respective dark controls. As illustrated by mass spectroscopic and chemical analyses, tetracycline was proposed to be mainly transformed to amide (ineffective in inducing ARGs) with the presence of clays by reaction with self-photosensitized singlet oxygen (1O2), while the humic substances might catalyze the production of another two demethylated and/or deaminated compounds (still effective in inducing ARGs) in addition to the amide compound via reaction with triplet excited state dissolved organic matter (3DOM*). As clay minerals and humic substances are important soil constituents and ubiquitously present in surface environments, the observed clay and humic-dependent photooxidation pathways of tetracycline and the differing selective pressures of the associated products highlight the need for monitoring the transformation compounds of antibiotics and provide critical insight into the development of antibiotic treatment protocols.

Photochemistry of N-aryl and N-alkyl dibenzothiophene sulfoximines.

N-phenyl dibenzothiophene sulfoximine has been demonstrated to produce phenyl nitrene and dibenzothiophene S-oxide upon irradiation with UV-A light, and dibenzothiophene S-oxide upon further irradiation releases triplet atomic oxygen. Thus, N-phenyl dibenzothiophene sulfoximine exhibits a rare dual-release capability in its photochemistry. In this work, N-substituted dibenzothiophene sulfoximine derivatives are irradiated with UV-A light to compare their photochemistry and quantum yield of dibenzothiophene S-oxide production with that of N-phenyl dibenzothiophene sulfoximine. Both N-aryl and N-alkyl derivatives of dibenzothiophene sulfoximine are examined to observe their effects on the quantum yield of the photolysis reaction. Adding electron withdrawing N-aryl substituents is shown to increase the quantum yield of dibenzothiophene S-oxide production, while adding electron donating N-aryl substituents is shown to decrease the quantum yield. The quantum yield was slightly lowered or not increased by most N-alkyl substituents. Furthermore, the quantum yield was not augmented by branching and steric hindrance effects associated with the N-alkyl substituents. These results suggest that electronic modulation of the sulfoximine bonds affects the observed photolysis reaction.

Influence of duty cycle on the physicochemical characteristics of an AC-driven argon plasma jet and its impact on hydrogen peroxide production and cell viability

This paper investigates how the duty cycle influences the production of hydrogen peroxide (H2O2) in an alternating current (AC)-driven plasma jet. H2O2 is a major reactive oxygen species produced by plasma jets in medicine and is a biological important molecule because it can intervene in cellular signaling processes important for disease treatment. In this study, duty cycles were varied from 9% to 72%, which correlated with an increase in the plasma’s dissipated power and UV photon energy density, and consequently an increase in the production of high energy plasma components important for producing H2O2 through electron collision and UV photolysis reactions. Cell media treated with the plasma jet at higher duty cycles correlated with a decrease in the viability of HaCaT keratinocyte skin cells. The AC-driven plasma jets were shown to be operated optimally at a biocompatible gas temperature of below 40 °C whilst still maintaining efficiency in H2O2 production. Overall, the data presented in this study might find use for the future of optimization of the electrical properties of AC-driven plasma jets in plasma medicine.

Reaction Kinetics of CH2OO and syn-CH3CHOO Criegee Intermediates with Acetaldehyde.

Criegee intermediates exert a crucial influence on atmospheric chemistry, functioning as powerful oxidants that facilitate the degradation of pollutants, and understanding their reaction kinetics is essential for accurate atmospheric modeling. In this study, the kinetics of CH2OO and syn-CH3CHOO reactions with acetaldehyde (CH3CHO) were investigated using a flash photolysis reaction tube coupled with the OH laser-induced fluorescence (LIF) method. The experimental results indicate that the reaction of syn-CH3CHOO with CH3CHO is independent of pressure in the range of 5-50 Torr when using Ar as the bath gas. However, the rate coefficient for the reaction between CH2OO and CH3CHO at 5.5 Torr was found to be lower compared to the near-constant values observed between 10 and 100 Torr. Furthermore, the reaction of syn-CH3CHOO with CH3CHO demonstrated positive temperature dependence from 283 to 330 K, with a rate coefficient of (2.11 ± 0.45) × 10-13 cm3 molecule-1 s-1 at 298 K. The activation energy and pre-exponential factor derived from the Arrhenius plot for this reaction were determined to be 2.32 ± 0.49 kcal mol-1 and (1.66 ± 0.61) × 10-11 cm3 molecule-1 s-1, respectively. In comparison, the reaction of CH2OO with CH3CHO exhibited negative temperature dependence, with a rate coefficient of (2.16 ± 0.39) × 10-12 cm3 molecule-1 s-1 at 100 Torr and 298 K and an activation energy and a pre-exponential factor of -1.73 ± 0.31 kcal mol-1 and (1.15 ± 0.21) × 10-13 cm3 molecule-1 s-1, respectively, over the temperature range of 280-333 K.

Pollutant Photodegradation Affected by Evaporative Water Concentration in a Climate Change Scenario.

Evaporative water concentration takes place in arid or semi-arid environments when stationary water bodies, such as lakes or ponds, prevalently lose water by evaporation, which prevails over outflow or seepage into aquifers. Absence or near-absence of precipitation and elevated temperatures are important prerequisites for the process, which has the potential to deeply affect the photochemical attenuation of pollutants, including contaminants of emerging concern (CECs). Here we show that water evaporation would enhance the phototransformation of many CECs, especially those undergoing degradation mainly through direct photolysis and triplet-sensitized reactions. In contrast, processes induced by hydroxyl and carbonate radicals would be inhibited. Our model results suggest that the photochemical impact of water evaporation might increase in the future in several regions of the world, with no continent likely being unaffected, due to the effects of local precipitation decrease combined with an increase in temperature that facilitates evaporation.

The Impact of Extended H2O Cross Sections on Temperate Anoxic Planet Atmospheres: Implications for Spectral Characterization of Habitable Worlds

JWST has created a new era of terrestrial exoplanet atmospheric characterization, and with it, the possibility to detect potential biosignature gases like CH4. Our interpretation of exoplanet atmospheric spectra, and the veracity of these interpretations, will be limited by our understanding of atmospheric processes and the accuracy of input modeling data. Molecular cross sections are essential inputs to these models. The photochemistry of temperate planets depends on photolysis reactions whose rates are governed by the dissociation cross sections of key molecules. H2O is one such molecule; the photolysis of H2O produces OH, a highly reactive and efficient sink for atmospheric trace gases. We investigate the photochemical effects of improved H2O cross sections on anoxic terrestrial planets as a function of host star spectral type and CH4 surface flux. Our results show that updated H2O cross sections, extended to wavelengths >200 nm, substantially impact the predicted abundances of trace gases destroyed by OH. The differences for anoxic terrestrial planets orbiting Sun-like host stars are greatest, showing changes of up to 3 orders of magnitude in surface CO levels, and over an order of magnitude in surface CH4 levels. These differences lead to observable changes in simulated planetary spectra, especially important in the context of future direct-imaging missions. In contrast, the atmospheres of planets orbiting M-dwarf stars are substantially less affected. Our results demonstrate a pressing need for refined dissociation cross-section data for H2O, where uncertainties remain, and other key molecules, especially at mid-UV wavelengths >200 nm.

Triplet-Triplet Annihilation Upconversion-Based Photolysis: Applications in Photopharmacology.

The emerging field of photopharmacology is a promising chemobiological methodology for optical control of drug activities that could ultimately solve the off-target toxicity outside the disease location of many drugs for the treatment of a given pathology. The use of photolytic reactions looks very attractive for a light-activated drug release but requires to develop photolytic reactions sensitive to red or near-infrared light excitation for better tissue penetration. This review will present the concepts of triplet-triplet annihilation upconversion-based photolysis and their recent in vivo applications for light-induced drug delivery using photoactivatable nanoparticles.

Spectroscopic Identification and Photochemistry of Astrochemically Relevant Phosphorus-bearing Molecules [O, C, N, P] and [2O, C, N, P

Diatomic molecules phosphorus monoxide (PO) and phosphorus mononitride (PN) are the main reservoirs of gas-phase phosphorus in interstellar and circumstellar environments, indicating the possibility of forming new phosphorus-bearing molecules through reactions with other interstellar species. To explore the astrochemistry of PO and PN, new simple phosphorus-bearing molecules [O, C, N, P] and [2O, C, N, P] were generated in the gas phase and isolated in cryogenic matrices for characterization with matrix-isolation IR and UV/vis spectroscopy in combination with calculations at the CCSD(T)-F12a/VTZ-F12 level of theory. In an inert argon matrix, OPCN isomerizes to OPNC upon UV-light irradiation at 365 nm, followed by successive isomerizations to PNCO and POCN with concomitant dissociation to diatomic PN and CO under further irradiation at 193 nm. By analogy, the isomerization of O2PCN to O2PNC and OPNCO followed by fragmentation to OPN/CO and PN/CO2 occurs in the matrix upon irradiation at 193 nm. In a chemically active CO ice, the photolytic reaction of OPCN with CO yields CO2 and PCN, and O2PCN reacts with CO by forming OPCN and CO2, in which the photochemical networks for these P-bearing species linking the astrochemically important PN and PO have been proposed. The experimental identification of these phosphorus-bearing molecules is supported by quantum chemical calculations, and the spectroscopic data may aid in their detection in the interstellar and circumstellar medium.

Aquatic photolysis of high-risk fluorinated liquid crystal monomers: Kinetics, toxicity evaluation, and mechanisms

Despite the frequent detection of fluorinated liquid-crystal monomers (FLCMs) in the environment, the level of understanding of their fate, toxicity, and transformation remains insufficient. Herein, we investigated the degradation kinetics and mechanism of an FLCM (4-cyano-3-fluorophenyl 4-ethylbenzoate, CEB-F) under ultraviolet (UV) photolysis in aquatic environment. Our findings demonstrated that the UV photolysis of CEB-F followed first-order kinetics. Photodegradation products were identified using liquid chromatography with mass spectrometry, and detailed reaction pathways were proposed. It is postulated that through the attack of reactive oxygen species, hydroxylation, and CO/C-F bond cleavage, CEB-F gradually degraded into small molecular compounds, releasing fluorine ions. Acute immobilization tests with Daphnia magna (D. magna) revealed significant acute toxicity of CEB-F, with LC50 values ranging from 1.023 to 0.0536 μM over 24 to 96 h, emphasizing the potential high risk of FLCMs in aquatic ecosystems if inadvertently discharged. Interestingly, we found that the toxicity of CEB-F photolysis reaction solutions was effectively reduced. Through catalase and acetylcholinesterase activities analysis along with molecular docking simulation, we proposed differences in the underlying toxicity mechanisms of CEB-F and its photolysis products to D. magna. These findings highlight the potential harmful effects of FLCMs on aquatic ecosystems and enrich our understanding of the photolysis behavior of FLCMs.

Solar Hydrogen Production by Artificial Photosynthesis in Photoreactor for Sustainable Mobility

The thermo-industrial human society is mainly based on fuels. Currently, societies are fully dependent on fossil fuels which cause climate change that threaten human race. Solar fuels are well suited technologies to face these challenges. Long-term solar energy storage based on chemical fuel production from water (and potentially CO2) has a significant importance to decarbonize our societies. Artificial photosynthesis is especially adapted to produce solar fuels, such as hydrogen, methane, ethanol, etc. This study focuses on hydrogen production. Water splitting with photolysis reaction is possible thanks to photocatalysts that absorb light and produce hydrogen. Modeling the hydrogen production is based on 3 main physics fields because the process is limited and controlled by radiative transfer. Electromagnetism is used to determine radiative properties. Then, radiative transfer allows to calculate photon absorption rates. Finally, the thermokinetic coupling law establishes a relation between photon absorption rate and hydrogen production rate. Experimentally, hydrogen production is operated in a dedi-cated laboratory-scale benchmark photoreactor. Photon flux density is controlled by a LED panel and hydrogen pressure variation is monitored with a pressure sensor. It is then possible to calculate experimental hydrogen production rates. The model predicts a non-linear thermo-kinetic coupling law, which fits well experimental results. Consequently, we demonstrated that the concept of incident solar flux density dilution is an important feature for process optimiza-tion. Several dilution technologies from TRL 3 to 5 are implemented in our laboratory thanks to the new PAVIN solar platform. They aim to validate high-efficiency technologies thanks to solar flux dilution.

The mechanism of photodegradation reaction of different dissociation forms of tetrabromobisphenol S in water with free radicals and the ecotoxicity evaluation of related products

Tetrabromobisphenol S (TBBPS) is a widely used brominated flame retardant that has attracted environmental concern due to its abundant presence in water. The objective of this study is to systematically analyze the direct photolysis and degradation mechanisms of TBBPS in two different dissociation forms in water, as well as to evaluate their toxicological effects induced by •OH, 1O2, and •NO2 radicals. The degradation mechanism of TBBPS is investigated with density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods, and the toxicity of the degradation products is assessed through toxicological studies. The results of the study indicate that the OH-addition and H-abstraction reactions are favorable pathways for •OH-induced TBBPS degradation. The H-abstraction reaction of TBBPS0 with •OH was more favorable than the •OH addition reaction. However, in the degradation of TBBPS−, the •OH addition reaction was favored over the H-abstraction reaction. Additionally, the indirect photolysis of TBBPS by 1O2 and •NO2 in water was found to be easier for TBBPS− compared to TBBPS0, with degradation mechanisms involving Br-substitution and NO2-addition reactions. The higher Ea values calculated indicate that the degradation of TBBPS by 1O2 and •NO2 in water has been a secondary reaction. The direct photolysis reaction pathway of TBBPS in water has involved the cleavage of the S1–C7 and S1–C16 bonds. For TBBPS0 in the S1/T1 states, the primary reaction pathway is the cleavage of the S1–C16 bond, while for TBBPS−, the primary reaction pathway is the cleavage of the S1–C7 bond. Furthermore, the computational toxicology results indicate a slight increase in the toxicity levels of most products, highlighting the significance of investigating the degradation byproducts of TBBPS in greater detail.

The tetracyanoborate anion as a building block for the heterocubane cluster cage [Cr4{B(CN)4}4]4.

The tetracyanoborate anion [B(CN)4]- (TCB) was utilized as a building block for the synthesis of polynuclear chromium carbonyl compounds upon photolytic reaction with [Cr(CO)6]. Up to four κN-coordinated cyano groups of TCB can be involved in binding to chromium, giving mixtures of [B(CN)4-x{CN-Cr(CO)5}x]- (x = 1-4; 1-4) and [{Cr(CO)4(B(CN)4)}2]2- (5). The reaction of [B(CN)4]- with fac-[Cr(CO)3(MeCN)3] led to isolation of salts of the tetraanionic heterocubane cage [{Cr(CO)3(B(CN)4)}4]4-.